Cross-validatory Selection of Test and Validation Sets in Multivariate Calibration and Neural Networks as Applied to Spectroscopy

(Note: The full text of this document is currently only available in the PDF Version )

Frank R. Burden, Frank R. Burden, Richard G. Brereton and Peter T. Walsh


Abstract

Cross-validated and non-cross-validated regression models using principal component regression (PCR), partial least squares (PLS) and artificial neural networks (ANN) have been used to relate the concentrations of polycyclic aromatic hydrocarbon pollutants to the electronic absorption spectra of coal tar pitch volatiles. The different trends in the cross-validated and non-cross-validated results are discussed as well as a method for the production of a true cross-validated neural network regression model. It is shown that the methods must be compared through the errors produced in the validation sets as well as those given for the final model. Various methods for calculation of errors are described and compared. The separation of training, validation and test sets into fully independent groups is emphasized. PLS outperforms PCR using all indicators. ANNs are inferior to multivariate techniques for individual compounds but are reasonably effective in predicting the sum of PAHs in the mixture set.


References

  1. D. A. Cirovic, R. G. Brereton, P. T. Walsh, J. A. Ellwood and E. Scobbie, Analyst, 1996, 121, 575 RSC.
  2. H. Martens and T. Naes, Multivariate Calibration, Wiley, New York, 1989 Search PubMed.
  3. A. Höskuldsson, J. Chemom., 1988, 2, 211.
  4. S. Wold, P. Geladi, K. Esbensen and J. Ohman, J. Chemom., 1987, 1, 41 CAS.
  5. B. R. Kowalski and M. B. Seasholtz, J. Chemom., 1991, 5, 129 CAS.
  6. C. Demir and R. G. Brereton, Analyst, 1997, 122, 631 RSC.
  7. P. Geladi and B. R. Kowalski, Anal. Chim. Acta, 1986, 185, 1 CrossRef CAS.
  8. P. J. Brown, J. R. Stat. Soc. Ser. B., 1982, 44, 287 Search PubMed.
  9. D. E. Rumelhart and J. L. McClelland, Parallel Distributed Processing, MIT Press, Cambridge, MA, 1986, vol. I Search PubMed.
  10. T. B. Blank and S. D. Brown, Anal. Chim. Acta., 1993, 277, 273 CrossRef CAS.
  11. B. Walczak and W. Wegscheider, Anal. Chim. Acta., 1993, 283, 508 CrossRef CAS.
  12. T. B. Blank and S. D. Brown, Anal. Chem., 1993, 65, 3081 CrossRef CAS.
  13. F. R. Burden, J. Chem. Inf. Comput. Sci., 1994, 34, 1229 CrossRef CAS.
  14. J. M. Deane, Multivariate Pattern Recognition in Chemometrics, illustrated by case studies, ed. Brereton, R. G., Elsevier, Amsterdam, 1992, ch. 5 Search PubMed.
  15. M. J. Stone, J. R. Stat. Soc. Ser. B., 1974, 36, 111 Search PubMed.
  16. S. Wold, Technometrics, 1978, 20, 397.
  17. W. J. Krzanowski, Biometrics, 1987, 44, 575 Search PubMed.
  18. P. J. Gemperline, J. Chemom., 1989, 3, 549 CAS.
  19. The MathWorks Inc., MA, USA.
Click here to see how this site uses Cookies. View our privacy policy here.